Composite materials for fluid treatment

ABSTRACT

This invention relates generally to composite materials and to devices which may alter fluid parameters. Devices incorporating the composite materials of the invention are used to deliver, remove, and generate, fluid treatment agents, and combinations thereof. These materials and devices are applicable to many different fluid processing situations including drinking water treatment, wastewater treatment, emission treatment, pollution cleanup, and sensing fluid composition. In its more particular aspects, the invention relates to the field of composites that may be widely tailored for many different treatment applications.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates generally to composite materials and to devicesthat may alter fluid parameters. Devices incorporating the compositematerials of the invention are used to deliver, remove, and generatefluid treatment agents (naturally occurring and synthetic chemical andbiological agents), and combinations thereof. These materials anddevices are applicable to many different fluid treatment situationsincluding those targeting drinking water, process fluids, fuels andemission, beverage production, cleaning operations, and sensing fluidcomposition. In its more particular aspects, the invention relates tothe field of multifunctional composite materials that may be tailoredfor many different fluid treatment applications.

2. Description of Related Art

Common Fluid Treatment Art

The treatment of fluids involves the removal of dissolved or suspendedcontaminants, the modification of fundamental parameters such as pH,dissolved gases, dissolved solids content, and temperature, and theincorporation of chemical and biological agents. Standard fluidtreatment practice directed at these goals involves the use of manydifferent treatment agents, devices, and techniques. Treatment agentsare commonly applied in all three states, gas, liquid, and solid. Thenature of the contaminant that must be removed or agent that must beadded and the allowable cost of the operation controls the choice oftreatment, agent, device, and methods used. Fluids are treated for awide range of applications including breathing, cleaning, ingestion,cooling, and direct participation in industrial chemical and biologicalprocesses.

Delivery of Fluid Treatment Chemicals

Fluid treatment agents are added to fluids to remove contaminants,chemically convert contaminants, and to modify fluid parametersincluding pH and the composition of dissolved components. For example,chlorine containing compounds are useful for disinfecting fluids and thecontainers and conduits used to manage the fluids.

Depending upon the scale of the application, the technical experience ofpersonnel conducting the treatment process, and the allowable costs,either solid, liquid, or gaseous forms of chlorine are used. Additionalfluid treatment examples include the dosing of flocculating agents toremove small particulate matter suspended in a fluid and the injectionof carbon dioxide for beverages production.

Delivery of solid, liquid or gaseous fluid treatment agents to fluids iscomplicated and requires significant technical experience to completesafely and efficiently. Injection and dosing systems require thecombination and optimization of well characterized solutions oftreatment agents, pumps, piping or tubing, flow control devicesincluding valves, and often a power source. Typically, the equipmentcosts and technical skill required to install, operate, and maintaininjection and dosing equipment limits the number of suitable applicationsites. Additionally, incorrect setting of equipment often damages orsubstantially decreases the lifetime of equipment positioned downstreamof the dosing operation.

Furthermore, many dosing and injection operations utilize reservoirscontaining concentrated forms of the treatment agents. These reservoirsmay pose safety hazards to both personnel who operate the equipment orthose in the vicinity and to equipment that contacts these agents.Spills, splashing, and leaks often require specialized cleanup agents,procedures, and often a distinct team of specially trained personnel. Asa result, all fluid dosing and injection systems require constantsupervision in order to effectively maintain operations.

Chemical Generation and Delivery

Several important fluid treatment agents may not be stored effectivelyand must be generated at the location of treatment. Examples include,the on-site generation of chlorine dioxide and ozone. Both are valuableoxidizing agents that may disinfect, breakdown organic compounds, andreact with dissolved inorganic compounds. Flocculating agents based onhydroxide precipitates including those containing aluminum and iron arealso commonly generated on site to maximize their particulate removalefficiencies. Safety is also a consideration. Transport of reactionprecursors in pressurized and concentrated forms is typically hazardousand a significant drawback to the technology.

Chemical and Biological Agent Collection, Sampling, and Detection

There are certain fluid contaminants that pose a hazard at extremely lowconcentrations. Examples include biological agents, nerve agents, andheavy metals. Since many of these contaminants accumulate in the bodyand fluid treatment components over time it is important to employdetection methods that are sensitive to very low concentrations of theseagents. Commonly some type of contaminant concentrating technique isused to retain and accumulate the agent to facilitate qualitative aswell as quantitative analysis. Both solid phase adsorption and liquidbased extraction techniques are used for removing contaminants from thefluid and concentrating. Analysis of the concentrated contaminant(s) mayinvolve stripping the contaminant from the concentrating medium,analyzing the collection media directly, or combinations thereof.

Application Space

A wide range of industrial processes and consumer activities involve theuse of fluids. In all cases fluids must be tailored for the specificapplication. These fluids are either prepared and packaged for directuse or equipment and products are fabricated that modify the fluid forits desired purpose at the point of use. Beverage products prepared foringestion require fluids to be initially purified and then formulatedwith agents to impart flavor, color, or nutritional benefit. Examplesinclude commercially available ready-to-drink beverages as well as tapwater that is treated before entering a complex distribution system.Similar situations exist for pharmaceutical and medical solutionpreparation.

Many companies produce products that treat gases and liquids at thepoint of use or the point of entry into an industrial facility, aresidence, or the environment. Common examples include breathing air anddrinking water. Treatment products for these fluids vary tremendously infunction, scale, and cost. In recent years, the desire for airfiltration in the home has become more popular as a need has beendemonstrated. Products with increasing sophistication are now available,addressing the concerns of both energy efficiency and indoor airquality. Many breathing air and drinking water applications sharecontaminant types and removal requirements.

Consumers use many types of household chemicals to modify fluids forcleaning in and around the household. Consumers also use many types ofsolutions for maintaining health and appearance including solutionsspecialized for eye care, lens care, dental care, and oral care.Additionally, leisure water activities including the use of pools andspas require fluid treatment on a continual basis.

Many industries must treat influent and effluent fluids in bulk. Ingeneral, both air and water emissions from industry must be of a higherquality than the original source. These include those that treatdrinking water, prepare food and beverages, generate power, controlequipment temperature, process chemical and biological agents includingfermentation processing and petroleum component separation.Pharmaceutical and medicinal solutions of gases and liquids require bothpurification and active agent incorporation. Similarly, the removal ofcontaminants from breathable air in hospitals and clean rooms, whereultrapurified air is required, and in environments where air isrecirculated, such as aircraft, spacecraft, individual protective suits,small group protective structures, and automobiles, is also an importantapplication for fluid treatment.

New materials and devices that may improve the function and capacity ofstandard treatment operations as well as increase the safety and costeffectiveness are highly desired.

SUMMARY OF THE INVENTION

To this end, novel composite materials and methods for fabricating thesecomposite materials have been discovered. These materials and devicescontaining these materials incorporate the beneficial aspects of bothsolid and liquid fluid treatment agents. The method and process of theinvention facilitates the generation of a wide range of compositematerials and devices including those which may be used for, removingdissolved and suspended contaminants, chemically reacting with dissolvedor suspended contaminants, delivering chemical and biological agents,generating dissolved agents for further application, generating solids,liquids, and gases for a broad range of applications. Likewise, thematerials and devices of the invention facilitate concentrating,storing, detecting, and degrading contaminants that are present ingases, liquids, and aerosols, at very low concentrations.

The composite materials and devices of the invention may be used in amanner that directs or controls fluid flow and composite materialcontact. Specifically, by controlling the composition of the material,fluid may be directed through the material, across the surface of thematerial, or a combination thereof. Manipulating flow rates allowscontact time between fluid and composite to be controlled, and theselectivity of treatment application.

Composite materials and devices of the invention may be generated inwidely varying shapes and sizes, and with functions that may beinfinitely tailored and tuned for specific applications. The inventionis scale independent as it may be utilized in very large as well as verysmall applications. The materials and devices of the invention maycontain a broad range of fluid treatment agents for treating gases,liquids, and aerosols. Likewise, these materials and devices may containa broad range of fluid additives commonly delivered into fluids forindustrial and consumer application.

The composite materials and methods of producing materials and devicesof the invention, incorporate solid materials that have both fluidabsorbing and fluid expanding characteristics. These materials may beused independently or combined with materials that do not expand whenexposed to fluids. Composite materials may be generated by combiningfluid expanding solids and single composition liquids, by combiningfluid expanding solids and liquid mixtures, by combining fluid expandingsolids and liquids with dissolved or suspended agents, by combiningfluid expanding solids and liquid mixtures which, when exposed tosolids, liquids, or gases, generate insoluble agents, by combining fluidexpanding solids and liquid mixtures which are then exposed to solids,liquids, or gases generate liquids or gases, by combining fluidexpanding solids and liquid mixtures that generate soluble agents,insoluble agents, and combinations thereof, when exposed to radiation orthermal energy. The composite materials may carry chemical andbiological agents in the fluid used to expand the solid, on thematerials surface, or a combination thereof. Composite materials may befurther tailored by incorporating material that does not expandsubstantially in the presence of fluid. These non-expanding materialsmay serve multiple functions in the composite including spacing, poregeneration, fluid storage and fluid treatment.

The materials and processes of the invention may be used to prepare awide range of devices with significant consumer, industrial, space,humanitarian, and defense application. In preferred applications thecomposite materials are fabricated in the form of blocks, tubes, sheets,fibers, films, or as isolated particles and are used to, modify theproperties of fluids through agent removal, conversion, addition, or acombination thereof, and sensing of fluid composition. The materials andmethods of the invention provide a means of combining many standardfluid treatment operations, processes, and materials into a singlecomposite material. In many cases, the efficiency, safety, and economicsof the treatment process are improved. The materials and methods of theinvention allow greater device design flexibility that ultimately allowsdevices of new shapes and sizes to be applied in new locations as wellas to better fit into current application space. Equally important isthe manufacturing flexibility that the materials and methods of theinvention enable. Materials and devices may be fabricated and assembledby hand or adapted to high throughput equipment. The cost associatedwith materials and manufacturing may be adapted to many manufacturingenvironments and situations. Additionally, devices may be prepared onthe go, in the field, and in many cases serviced in a similar manner.

As indicated above, many types of solid-liquid combinations may begenerated with the materials and method of the invention. Thesematerials and devices incorporating these materials are immediatelyuseful in a broad range of fluid treatment applications. The materialsand methods of the invention greatly simplify the removal and deliveryof chemical and biological agents associated with fluids. Further thematerials and methods of the invention provide the capacity tosimultaneously employ both solids and liquids in the treatment offluids. Furthermore, the devices and methods of the invention improvethe safety, and reduce the complexity of many fluid treatment agentdosing and injection operations. The solids incorporated into thecomposite materials of the invention may be used for absorption,adsorption, chemical reaction, dissolution, and a combination thereof.The liquids incorporated into the composite materials of the inventionmay be used for absorption, adsorption, chemical reaction, dissolutionand a combination thereof. The combination of solids and liquidsprovides a platform for tailoring treatment materials where the solidsand liquids function synergistically.

A wide range of contaminants may be treated with the materials andmethods of the invention. These include naturally occurring andsynthetic organic and inorganic agents, in both dissolved andparticulate states, microorganisms in active and dormant states, andcombinations thereof.

Agents that may be delivered to fluids include naturally occurring andsynthetic organic and inorganic agents in dissolved and particulatestates, microorganisms in active and dormant states, and combinationsthereof.

The applications for the materials and devices of the invention may beroughly separated into two groups for description purposes but in nomanner limits the applications and fields where the materials anddevices of the invention are useful. In many cases, similar materialsand devices of the invention may be applied directly in both gas phaseand liquid phase applications.

The first group is the treatment of liquids including those associatedwith drinking water, waste water, beverage production, pharmaceuticaland semiconductor processing, chemical processing, biotechnology productprocessing, process streams that use catalysts, cleaning solutionpreparation, eye and lens care, dental and oral care, and toxinconcentration, detection, and degradation.

The second group is the treatment of gases including those associatedwith breathing air, residential air, industrial emissions, energyproduction, enclosed recirculated air systems, process streams that usecatalysts, and toxin concentration and detection.

In typical embodiments, the invention relates to a composite materialfor fluid treatment that consists of a fluid expandable material such asa natural or synthetic polymer or clay that carries a fluid with acomposition that is typically different than the fluid undergoingtreatment. The fluid contained by the expandable material and thereforethe composite material may or may not be removed from the compositematerial in the fluid treatment operation.

Typical embodiments may also include composite materials that aregenerated from a mixture of fluid expanding and fluid nonexpandingmaterials. The nonexpanding materials provide a dilution function, mayaffect porosity, and may also provide an extension of the compositematerial's fluid treatment function. Additionally, synergisticcombinations and complex multistage treatment functions are possible.Non-expanding solid materials include carbon, activated carbons, naturaland synthetic minerals, textiles, ion-exchange materials, resins,metals, catalysts, synthetic and natural molecules and polymers, and awide range of materials typically used in fluid treatment.

Typical embodiments may also include composite materials that containfluid soluble chemical and biological agents that provide a fluidtreatment function. Specifically, these agents are used to removecontaminants or modify the composition of the fluid contacting thematerial. The soluble agent may be included in the composite in adissolved or solid form.

Typical embodiments may also include composite materials that containfluid insoluble or slightly soluble chemical and biological agents thatprovide a fluid treatment function. Specifically, these agents are usedto remove contaminants or modify the composition of the fluid contactingthe material.

Typical embodiments may also include a support structure for thecomposite materials. The supports are porous in defined locations anddesigns and prepared from rigid, semi-rigid, or flexible materials andcombinations thereof. These supports may be prepared from synthetic aswell as natural materials.

Typical embodiments may also include a housing for the compositematerials and associated support structures, if any, as well as apassive or active system or mechanism for directing fluid into contactwith the composite materials. Examples would include deflectors, foils,pumps, blowers, and cyclones. These may also be combined with electriccharging devices and precipitating devices.

Typical embodiments may also include situations where the agentscontained by the composite material of the invention react throughexposure and contact with other agents in solid, liquid, or gaseous formand generate additional solid, liquid, or gaseous fluid treatmentagents. The combination of these agents and materials and the devicesthat control their contact are representative of devices of theinvention.

Typical embodiments may also include situations where the chemical orbiological agents removed from a contaminated fluid are accumulated(concentrated) over time for the purpose of fluid purification andcontaminant identification and quantitation. The materials and devicesof the invention are ideally suited for direct or indirect chemical andgenetic analysis, non-destructive and destructive spectroscopicanalysis, as well as other types of chemical analysis. Materials anddevices of the invention facilitate analysis in the laboratory as wellas in the field with a range of electronic and radiation based sensingmethods.

Typical embodiments may also include situations where the compositematerial serves as a tunable conduit between the fluid to be treated anda reservoir. The reservoir may contain fluid treatment agents fordelivery to the fluid requiring treatment, or it may serve as acollector for transfer of agents from the fluid requiring treatment, orcombinations thereof.

Typical embodiments for composite form may also include, blocks, sheets,webs, membrane, fibers, and individual particles or fibers that may bemoved through a fluid in continuous or semi-continuous fashion.Translation methods may include mechanical, magnetic, and electric fieldmanipulation, the use of gravity, or combinations thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a cross-sectional view illustrating a particular embodimentof the invention, namely a porous support (two-sides) containingcomposite material comprising fluid expandable material, expanded with afluid treatment agent and combined with an optional fluid non-expandingmaterial. An appropriate housing is positioned in a cross-flowfiltration geometry that connects a conduit containing the fluid to betreated and a conduit or container that collects and transfers treatedfluid.

FIG. 1B is a cross-sectional view illustrating a particular embodimentof the invention, namely a porous support (two-sides) containingcomposite material comprising fluid expandable material, expanded with afluid treatment agent and combined with an optional nonexpandingmaterial. An appropriate housing is positioned in a flow throughgeometry.

FIG. 1C is a cross-sectional view illustrating a particular embodimentof the invention, namely a porous support (two-sides) containingcomposite material comprising fluid expandable material, expanded with afluid treatment agent and combined with an optional fluid nonexpandingmaterial. An appropriate housing is positioned in a cross-flowfiltration geometry or a flow-through geometry and connected to areservoir that contains a fluid treatment agent.

FIG. 1D is a cross-sectional view illustrating a particular embodimentof the invention, namely a porous support (two sides) containingcomposite material comprising fluid expandable material, expanded with afluid treatment agent and combined with an optional nonexpandingmaterial. An appropriate housing is positioned in a geometry that maycontrol fluid flow based on porosity and changing porosity of thecomposite material.

FIGS. 2A and 2B are cross-sectional views illustrating particularembodiments of the invention, namely a porous support (cartridge)containing composite material comprising fluid expandable material,expanded with a fluid treatment agent and combined with an optionalnonexpanding material. The cartridge containing the composite materialcontains a central bore that allows radial flow through the material ofthe invention and out of the cartridge housing. FIG. 2B includes anextension of the central bore outside of the composite material. Byadjusting the length of this extended central bore fluid compositematerial contact may be controlled. Choice of cartridge housing porositymay also be used in conjunction with central bore location to fine tunefluid treatment parameters. The cartridge housing is contained in alarger vessel that connects to tanks and conduits that direct fluid flowin and out of the vessel.

FIGS. 3A and 3B are cross-sectional views illustrating particularembodiments of the invention, namely a porous support (two-sides)containing composite material comprising fluid expandable material,expanded with a fluid treatment agent and combined with an optionalnonexpanding material and presented in a planar format that is typicalof air filters. The planar format is a flow through design that allowsmany different thicknesses to be used. FIG. 3 b extends the embodimentto include the wrapping of planar sheets containing the materials of theinvention around a central bore. This geometry allows cross-flow as wellas flow through in a radial geometry.

FIGS. 4A and 4B are cross-sectional views illustrating particularembodiments of the invention, namely a porous drop zone (four sides), areservoir containing composite material comprising fluid expandablematerial, expanded with a fluid treatment agent, and including acollection basin. In this embodiment expanded composite particles movethrough the drop zone by the force of gravity. While moving through thezone the particles collect contaminants that are analyzed in thecollection basin or are removed and analyzed. FIG. 4A presents theembodiment in a rectangular format while 4B presents the embodiment in acylindrical format. In both orientations the dropped particles may alsobe guided using fibers, meshes, or screens. This embodiment is easilyextended to fibers and sheets that are pulled manipulated the fluidcontact zone.

FIGS. 5A is a cross-sectional view illustrating a particular embodimentof the invention, namely a porous housing (bag) containing compositematerial comprising fluid expandable material, expanded with a fluidtreatment agent and combined with an optional nonexpanding material andpresented in “tea-bag” format that is commonly available forconsumer-use in preparing beverages and introducing fragrances into theair. In this format beverages may be prepared based on the contents ofthe composite material. In some cases this embodiment includes thetreatment of fluid contaminants present in the fluid used to prepare thebeverage.

FIGS. 5B is a cross-sectional view illustrating a particular embodimentof the invention, namely loose composite materials (fibers, particles)comprising fluid expandable material, expanded with a fluid treatmentagent and combined with an optional nonexpanding material and presentedin “loose-coffee-maker” format that is commonly available forconsumer-use in preparing beverages. In this format beverages may beprepared based on the contents of the composite material. In some casesthis embodiment includes the treatment of fluid contaminants present inthe fluid used to prepare the beverage.

DETAILED DESCRIPTION OF THE INVENTION

As indicated above in the Summary, in its general embodiments theinvention relates to composite materials and devices incorporating thecomposite materials that combine fluids and fluid expandable materials.General embodiments also include the mixture of fluid expandable andnon-fluid expandable materials into composites. Devices based on thesegeneral embodiments may be fabricated by adding the fluid expanding andoptionally non-expanding materials to porous containers or supports andsubsequently to housings that provide fluid contact. These porouscontainers may take the form of canisters, coatings, membranes, andsheets and may be combined, wrapped, or prepared in a wide range ofgeometric structures. Devices may be produced in any shape or size andmay be rigid or flexible. The materials of the invention may be utilizedin direct contact with membrane materials including those incorporatinghollow fibers.

Fluid flow through or across the composite material may be tuned by theselection of components, size of the granular or fibrous fluid expandingand optional nonexpanding components and the porous structural support,if necessary for the application. As used herein, the term “compositematerial” does not denote any particular geometrical shape. Nonlimitingexamples of “composite materials” as this term is intended to be usedinclude tubes and annular rings, as well as more conventionalgeometrical solids. Material formed into flexible composite materials isparticularly suitable for use in pipes or tubes that serve as the fluidfilter medium and in combination with membrane systems including hollowfiber systems.

One of the desirable features of composite materials generated with theinvention is that devices may be formed into any desired shape. Thisprovides ease of handling and extremely high scalability. For example, acomposite material may be formed into a monolith or wrapped sheet thatfits into conventional fluid treatment housings. It may be shaped toprovide fluid treatment as part of a portable or personal system orshaped to provide emission treatment for large industrial sites. Thematerial may be formed into several different pieces, through whichfluid flows in series or in parallel. Sheets or membranes of thecomposite purification material may also be formed. The rigidity of thepurification material and subsequent devices, whether in block form orin sheet/membrane form, may be altered through inclusion of flexiblesupport structures that contain the expanding and optional non-expandingmaterial.

The expanding material may be in the form of particles ranging in sizefrom 0.05 microns through 100 millimeters, fibers with diameters of 0.05microns through 100 millimeters, or combinations thereof. The optionalnon-expanding material may have similar sizes.

Preferred and applicable expanding fluid treatment matter includesmaterial that expands as a result of absorption of fluids (either gasesor liquids) and may be generated from a range of synthetic and naturalmaterials. These materials include synthetic and natural polymers, aswell as certain natural and synthetic clays.

The class of materials known as “superabsorbents” is particularlysuitable in this regard. Superabsorbents are natural, synthetic, ormixed polymers that are not fully cross-linked. They may be classifiedas polyelectrolyte or nonpolyelectrolyte types as well covalent, ionic,or physical gelling materials. These materials have the capacity toabsorb many times their own volume in fluid. Examples of syntheticmaterials include polyacrylic acids, polyacrylamides, poly-alcohols,polyamines, and polyethylene oxides. The composite superabsorbentmaterial may also be selected from derivatives of polyacrylic acids,polyacrylamides, poly-alcohols, polyamines, polyethylene oxides,cellulose, chitins, gelatins, starch, polyvinyl alcohols and polyacrylicacid, polyacrylonitrile, carboxymethyl cellulose, alginic acids,carrageenans isolated from seaweeds, polysaccharides, pectins, xanthans,poly-(diallyldimethylammonium chloride), poly-vinylpyridine,poly-vinylbenzyltrimethylammonium salts, polyvinylacetates, polylacticacids, or combinations thereof. The composite material may alsocomprises a material selected from resins obtained by polymerizingderivatives of acrylic acid or resins obtained by polymerizingderivatives of acrylamide.

Biodegradable materials that are suitable include cellulose derivatives,chitins, and gelatins. Additionally mixtures of synthetic polymer andnatural polymers either as distinct chains or in copolymers may be usedto generate these absorbent materials. Examples include starchpolyacrylic acid, polyvinyl alcohols and polyacrylic acid, starch andpolyacrylonitrile, carboxymethyl cellulose, alginic acids carrageenansisolated from seaweeds, polysaccharides, pectins, xanthans,poly(diallyldimethylammonium chloride), polyvinylpyridine,polyvinylbenzyltrimethylammonium salts, cellulose, alginic acids,carrageenans isolated from seaweeds, polysaccharides, pectins, xanthans,starch, or combinations thereof, polyethyleneglycol, a polylactic acid,a polyvinylalcohol, a co-polylactideglycolide, cellulose, alginic acids,carrageenans isolated from seaweeds, polysaccharides, pectins, xanthans,and starch.

As those experienced in the art will understand the process ofcrosslinking polymer chains derived from either any source orcombinations of sources, are variable and will affect the magnitude offluid absorption, and the types of fluids that may be absorbed.

Additionally those experienced in the art will understand that molecularcharacteristics such as polymer chain composition, functional groupposition and distribution as well as polymer molecular weight anddistribution will effect performance, and will know how to modify theseparameters to vary the properties of the resulting composite consistentwith the basic tenets of the invention. Further those experienced in theart will understand the expansion or final volume capacity of a materialis also subject to the type and composition of the fluid in which thematerial is exposed.

Inorganic sources of expanding particles include aluminosilicates,smectic or montmorillinite clays, and a preferred clay, bentonite.

Preferred and applicable optional non-expanding materials includenaturally occurring, synthetic, and recycled materials. Suitableoptional non-expanding materials include insoluble phosphate containingminerals selected from calcium phosphates, iron phosphates, manganesephosphates, aluminum phosphates, magnesium phosphates, magnesiumphosphates, silver phosphates, copper phosphates, zinc phosphates,zirconium phosphates, calcium monophosphates, diphosphates, tricalicumphosphates, octaphosphate, metaphosphates, metal oxides selected such asaluminum oxides, iron oxides, magnesium oxides, calcium oxides,manganese oxides, zinc oxides, copper oxides, titanium oxides, siliconoxides, aluminum containing minerals such as, alumina bauxite, kaoline,iron containing minerals such as iron oxide amorphous hydrous ferricoxide, maghemite, hematite, goethite, lepidocrocite, manganesecontaining minerals such as, manganese oxide, pyrolusite, silicacontaining minerals including, silica, quartz, metals such as iron,copper, manganese, silver, gold, platinum, rhodium, zinc, alloysprepared from iron, copper, zinc, carbon, chromium, manganese, nickel,carbonates such as calcium carbonate, magnesium carbonate, ironcarbonate, aluminum carbonate, sulfates including magnesium sulfate, andcalcium sulfate, hydroxides such as aluminum hydroxide, iron hydroxide,magnesium hydroxide, calcium hydroxide, and copper hydroxide. Syntheticand natural fibers, including strings, yarns and textiles including,cotton, wool, polypropylene, rayon, polyester, nylon, acrylic are alsoapplicable. Ion exchange material is a preferred material and includesresins selected from functionalized styrenes, vinylchlorides, divinylbenzenes, methacrylates, acrylates, or mixtures, copolymers, and blendsthereof. Natural and synthetic zeolites such as clinoptilolite andglauconate are preferred.

Catalytic materials generated from these components are quite common andthese are applicable in all known forms. Those experienced in the artwill recognize that the deposition of molecules containing active sitesthat include metals and atoms and nanocomposites of metals andsemimetals on the surface of support materials are immediatelyapplicable.

Fast and slowly dissolving as well as time release materials are alsoavailable in particulate and fiber form and these are applicable asnon-expanding materials. Preferred materials include those that impartflavor, sweetness, medicinal benefits and dietary benefits. Furthermorenutrients such as nitrogen, potassium, and phosphorus containingmaterials are preferred. Many of these materials have been designed intoslow dissolving and time released formats. Those experienced in the artwill recognize the ease of applying these materials in the currentinvention.

Those experienced in the art will also understand that both theexpanding materials and the optional non-expanding materials may besurface modified with a range of compounds and different bindingmethods. Examples of preferred surface modification chemicals includechemical agents selected from 3-acryloxypropylotrichlorosilane,3-acrlyoxypropylotrimethocysilane, Allyltrichlorosilane,allyltrimethoxysilane, allyltriethoxysilane,3-bromopropylotrichlorosilane, 3-bromopropyltrimethoxysilane,(p-chloromethyl)phenyltrichlorosilane),(p-chloromethyl)phenyltrimethoxysilane,1-trimethoxysilyl-2-2(p,m-chloromethyl)-phenylethane,chloromethyltrichlorosilane, chloromethyltriethoxysilane,2-chloroethyltriethoxysilane, 3-chloropropyltrichlorosilane,3-chloropropyl-trimethoxysilane, 3-glycidoxypropyltrimethoxysilane,3-iodopropyl trimethoxysilane, 3-isocyanatopropyltriethoxysilane,2-(diphenylphosphino) ethyltriethoxysilane,vinyltriacetoxysilane,vinyltrichlorosilane, vinyltriethoxysilane,vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane,3-mercaptopropyltriethoxysilane, N-(triethoxysilylpropyl) urea,3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxy silane,N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 2-(carbomethoxy)ethyltrichlorosilane, N-[(3-trimethoxysilyl)propyl]ethylenediaminetriacetic acid, trisodium salt, 3-cyanopropyltrichlorosilane,3-cyanopropyltriethoxysilane,2-(4-chlorosulfonylphenyl)ethyltrichlorosilane,2-(4-chlorosulfonylphenyl) ethyltrimethoxysilane, 2-(trimethoxysilyl)ethyl-2-pyridine, N-(3-trimethoxysilylpropyl)pyrrole,N-octadecyldimethyl-1(3-trimethoxysilyl) propyl]ammoniumchloride,N-trimethoxysilylpropyl-n,n,n-trimethyl ammoniym chloride,3-(trimethoxysilyl)propyldimethyloctadecylammonium chloride silanequaternary amine, chloropropyl trihydroxy silane, polyamines,polyamides, polyalcohols, polysaacharides, polyacrylamides,polyacrylates, humic acids, peptides, proteins, polorganozirconates,p-olyorganoaluminates, polysiloxanes, polysilanes, polysilazanes,polycarbosilanes, polyborosilanes, zirconium dimethacrulate, zirconiumtetramethacrylate, zirconium 2-ethylhexanoate, aluminum butoxides,aluminum diisopropoxide ethylacetoacetate, tetramethyldisiloxanes andderivatives thereof, tristrimethylsilylphosphate andtristrimethylsiloxyboron, polyamines such as poly(DADMAC), poly-DADM,polyamine-poly(DADMAC) blends, polyquartenary amines,inorganic-polyamine blends, and inorganic poly(DADMAC) blends, cationicstarch, cationic poly-methylmethacrylates, copolymers ofvinylimidazolium methochloride and vinylpyrrolidone, quarternizedvinylpyrrolidone/dimethyl-aminoethyl-methacrylate copolymer,polyethyleneimine, or combinations thereof.

Additionally, surface binding methods that provide the capacity ofimmobilizing genetic material, proteins, peptides, antibodies, andpharmaceutical agents are preferred means of modifying the surfaces ofboth the expanding and non-expanding materials. Those experienced in theart will recognize that numerous procedures exist for generating stablesurface coatings of these materials. Furthermore the ability toimmobilize genetic information as well as proteins and peptidesfacilitates the use of the materials of the invention in sensing andsensor development.

The materials and methods of the invention are unique in the capacity toexpand with a range of different fluids that are useful for fluidtreatment. Expandable materials may be expanded with synthetic andnatural fluids, inorganic, organic, and combinations of both, such asacids, bases, oxidizing agents, reducing agents, precipitating agents,polymerization agents, flocculating agents, surfactants, salts,halogens, peroxides, persulfates, carbonates, amines, polyamines,quaternary amines, medicinal agents, eye care agents, lens care agents,dental care agents, oral care agents, pharmaceutical agents,nutraceuticals, dietary supplements, alcohol or mixture of alcohols,fragrances, odor neutralizing agents, odor masking agents, disinfectingagents, preservatives, biocides, bacteriostats, fungistats, osmosticregulators, sequestering agents, chelating agents, and binderspesticides, insecticides, herbicides, phermones, and animal attractants,cleaning solutions, fatty acids, soaps, and sweetening agents.

Additionally, appropriate combinations of the listed agents with solventcombinations, and sequestering agents facilitates the expanding of theexpandable material with an extremely wide range of solution types andratios. Fluids used to expand the materials of the invention may bedelivered to the fluid that is to be treated or retained. Thoseexperienced in the art will recognize the compatibility issues betweenfluid types and dissolved species carried by the fluids. Further, thoseexperienced in the art will recognize that the nature and identity ofthe expandable material will vary in the presence of these fluid typesand the dissolved species carried by the fluids. Furthermore, thoseexperienced in the art will recognize that the properties of theexpandable materials will be modified as the concentrations of fluidsand dissolved species they contain vary throughout the course of fluidtreatment. Furthermore, those experienced in the art will recognize thatphysical parameters including temperature and irradiation will effectthe materials of this invention.

The materials and methods of the invention are further unique in thecapacity to generate fluid treatment compounds from soluble precursorsassociated with the fluid expanding material, optional nonexpandingmaterials, or combinations of both. By expanding the fluid expandablematerial with solutions containing soluble chemical species andsubsequently exposing the material to appropriate agents and physicalprocesses, insoluble or reduced solubility materials may be formed. Thismethod of material fabrication allows many materials to be generated ina form that maintains certain aspects of their function. Examples ofpreferred materials that may be formed in this manner include insolubleminerals such as phosphates, sulfates, sulfides, carbonates, chlorides,bromides, iodides, fluorides, oxides, hydroxides, silicates, cyanides,thiocyanates, arsenates, oxalates, chromates, manganates, reducedmetals, and combinations thereof. Further, organic and biologicalreactions may be used to generate useful fluid treatment agents in andassociated with the expandable fluid materials and optional nonexpandingmaterials. Furthermore, electrochemical, photochemical, and thermallyinduced reactions may be conducted in the materials of the inventionwhich allows the fabrication of unique materials. Examples include thesynthesis of polymers and the reduction of metals.

The materials and methods of the invention are further unique in thecapacity to generate agents such as gases and liquids containingreactive agents by contacting the fluid expanded materials with gas,liquid, and solid agents of combinations thereof. This capacity allowssafe and controlled reactions to occur. Agents that may be generatedwith these materials include gases, and liquids and fluids that containthe products of these reactions. Preferred reactions include those thatgenerate gases for disinfection, cleaning, energy production, breathing,and controlling atmospheric components. Likewise preferred applicationswhere liquids and dissolved agents are utilized include medicinal,dental, cleaning, disinfection, and power generation.

The porosity of the composite materials of the invention may be tunedthrough the choice of expandable and non-expandable materials, fluids,and dissolved or suspended materials. The porosity of the materials maybe tailored to allow complete absence of flow through the materialthrough complete passage. Those experienced in the art will understandthe contact time, bypass, and backpressure parameters that areassociated with these flow dynamics.

The composite materials of the invention are widely applicable to manyindustries, fluid treatment situations, and for the development ofproducts that serve the needs of consumers, healthcare, industry, anddefense related operations. The material of this invention requires noexpensive instrumentation or equipment, or significant expertise tofabricate. Expanding and optional non-expanding materials may be mixed,homogenously or heterogeneously in any ratio and composition and maysimply be added to a supporting structure of sufficient size andstrength to contain the composite. This facilitates the production ofmany different sizes, shapes, and designs.

The composite materials of the invention allow contaminants to beremoved from a fluid, converted to less toxic forms as well as collectedand concentrated for further analysis. Materials and devices of theinvention are also well suited for the delivery of agents to fluids. Thelatter capacity allows the materials to be used in fluid treatment forthe preparation of beverages, cleaning solutions, eye care solutions,lens care solutions, dental solutions, oral cavity treatment solutions,and agents for further reaction.

The invention has numerous advantages compared to former means ofcompleting many of these fluid treatment tasks. These include theelimination of electrical equipment such as pumps and technical know-howrequired to correctly dose agents into fluids in a stable and consistentfashion. When the fluid to be used in dosing applications is hazardousincorporation into the expandable materials increases the safety ofhandling the agent, eliminating the possibility of spills and leaks, andfacilitating neutralization and cleanup if a need existed. Whensolutions are prepared in correct ratios and used to expand thematerials of the invention they may be used as concentrates for theproduction of beverages, or cleaning solutions for fluids, surfaces,chemical toxins, teeth, dental structures, and contact lenses, as wellas treatment solutions for eyes, skin, hair and other body parts, withreduced concentrations. Accurate composite material preparation allowsaccurate solutions to be prepared in a safer and more controlled manner.Additionally, the materials of the invention may be used for sensing anddetecting microorganisms in fluid streams. The materials of theinvention may also be used for connecting a reservoir to a system forfluid treatment. The fluid expandable material provides a barrierbetween the fluid requiring treatment and a reservoir that contains afluid treatment agent. The properties of the composite material controlthe rate of agent transport between the reservoir and the fluid. Thereservoir may contain solid, liquid or gaseous agents. The materials ofthe invention may also be used to increase the safety of chemicalreactions that produce fluid treatment agents such as disinfectiongases, by allowing two solid materials (one true solid and one fluidexpandable carrier) to be combined instead of a hazardous liquid and asolid.

Those familiar with the art of fluid filtration will understand that thepore size and physical dimensions of the composite purification materialmay be manipulated for different applications and that variations inthese variables will alter flow rates, back-pressure, and the magnitudeof chemical and/or microbiological contaminant removal or delivery.Likewise those knowledgeable in the art will recognize that variationsin the percentages of each component of the composite purificationmaterial will provide variable utility. For example, increasing thepercentage of expanding matter in the composite purification materialwill result in a material having an increased pressure drop and lowerflow, while decreasing the percentage of expanding matter will result ina composite purification material having flow rate and pressure dropproperties closer to that of granular materials.

In one particular embodiment of the invention, the composite material isformulated to remove contaminants from a gas. Gas phase contaminants mayinclude acid gases formed during combustion processes, dry particulatematter, and aerosols. Many excellent materials and devices may begenerated by the materials and methods of the invention. As example, asuitable treatment material may be generated by expanding polyacrylicacid particles with an agent such as an aqueous solution of sodiumhydroxide or another hydroxide containing agent, and placing thematerial in a porous polyethylene container. A suitable example isprovided in FIG. 4A. When acid gases such as hydrogen chloride, carbondioxide, nitrogen oxides, sulfur oxides, and hydrogen cyanide contactthe composite media the gases are neutralized and the neutralizationproducts dissolved in the liquid matrix of the composite material.Likewise aerosols of aqueous solutions when contacting the compositemedia are absorbed into the matrix of the composite material as long asthe capacity of the individual particles has not been reached.Particulate matter depending upon size is adsorbed on the surface of thecomposite material, incorporated into the liquid matrix of the compositematerial, or combinations thereof. Particulate material is alsomechanically removed by interaction with the support structure for thecomposite material which can be constructed from membrane materials.Sensing an monitoring of hydroxide concentration in the composite can becompleted by a number of different methods including colorimetricindicators, and electrochemical sensors.

In another particular embodiment of the invention, the compositematerial detailed in the previous embodiment is used is used to removedissolved and particulate contaminants and modify the pH of water to beused for drinking. Drinking water contaminants include dissolved metalsand suspended particulate matter. Acidic pH water is corrosive toplumbing systems. When the contaminated low pH water is exposed to thecomposite media dissolved metal ions such as iron form insolublehydroxides that may be mechanically removed from the fluid. Additionallythese materials adsorb other dissolved contaminants including dissolvedmetals and organics. Suspended particulate matter is adsorbed on thesurface of the composite materials and mechanically removed from thefluid by both the support (container) and the pore size of the compositematerial. Finally, as the acid water contacts the composite material thewater is neutralized, raising the pH to acceptable levels. Sensing anmonitoring of hydroxide concentration in the composite can be completedby a number of different methods including colorimetric indicators, andelectrochemical sensors.

In another particular embodiment of the invention, the compositematerial detailed in the previous embodiment is used is used to removedissolved and particulate contaminants and modify the pH of water to beused for drinking, but is also connected to a reservoir. This reservoircontains a concentrated form of sodium hydroxide. An example of thedevice is provided in FIG. 1C. Drinking water contaminants includedissolved metals and suspended particulate matter. Acidic pH water isalso corrosive to plumbing systems. When the contaminated water isexposed to the composite media dissolved metal ions such as iron forminsoluble hydroxides that may be mechanically removed from the fluid.Additionally these materials adsorb other dissolved contaminantsincluding dissolved metals and organics. Suspended particulate matter isnot removed from the fluid stream, by the composite media, in thisembodiment. Finally, as the acid water contact the composite materialthe water is neutralized, raising the pH to acceptable levels. Thereservoir in this embodiment may be prepared using solid or liquidsodium hydroxide, or other hydroxide generating mechanism, includingthose based on electrochemical and electrode incorporation. Theproperties of the fluid being treated, the total area of the compositematerial as well as other physical and chemical parameters control themovement of treatment agent to the fluid. In this embodiment, there mayalso be removal of contaminants from the fluid undergoing treatment tothe reservoir. This depends upon the nature of the fluid, contaminant,and method of the invention.

In another particular embodiment of the invention, the compositematerial is prepared with a beverage concentrate for the production of abeverage. An aqueous solution containing a high concentration ofsweetening agents, natural and artificial flavorings, phosphoric acid,and coloring agents is used to expand polyacrylic acid particles. Whenthese composite materials are exposed to water, in devices as depictedin FIGS. 5A and 5B, the concentrated beverage agents contained in thecomposite are released, generating a beverage. In this embodiment,containment of the composite material is provided by a porous sheet(FIG. 5A) and by a porous mesh screen (FIG. 5B). In this embodiment,dissolved and suspended contaminants may also be removed by interactingwith the composite material as well as the support system provided forcontaining and/or isolating the composite material. As example, waterhardness ions and dissolved metal species may adsorb to the surface ofthe polyacrylic acid and to the support system for the device used tocontain the composite material. This embodiment may also be extended byincorporating a reservoir with the beverage concentrate. Likewise, thisembodiment demonstrates the ability to deliver other agents including,bacteriostatic and disinfection agents, medicinal agents, cleaningagents, eye care solutions, lens cleaning solutions, dental care andoral care solutions, solutions for neutralizing chemical toxins, andhealth and dietary agents.

In another particular embodiment of the invention, a composite materialis formed by generating insoluble fluid treatment compounds usingsoluble precursors contained by the expandable matter. Many differentinsoluble fluid treatment compounds may be generated through the methodof this invention. As a specific example, a water soluble sodiumphosphate compound may be used to expand polyacrylic-polyacrylamideparticles. When these particles are exposed to an aqueous solution ofcalcium chloride, calcium phosphate is generated. The composite materialmay be used directly for fluid treatment. An additional example includesthe expanding of the same polymer particles with an aqueous solution ofaluminum sulfate. When these particles are exposed to solutions withelevated pH, aluminum hydroxides are formed and the material may bedirectly used in fluid treatment.

In another particular embodiment of the invention, the compositematerial may be used to generate agents for fluid treatment such asgases. Many different gases are commonly injected into fluids fordifferent reasons. Carbon dioxide is injected for beverage production,chlorine dioxide and chlorine are injected for disinfection purposes,oxides of nitrogen are injected for medicinal purposes, and oxygen andnitrogen ratios are varied for respiratory purposes. Gases may also begenerated for power production and fuel cell operation. Gases are oftengenerated by the reaction of soluble chemicals, electrochemicalreactions, or through direct injection of the stored gas. In thisembodiment gases are generated either through chemical reaction betweenan agent contained by the composite material and a second reagent insolid, liquid, gaseous form or by contacting an electrode with thecomposite media for the same purpose. Those experienced in the art willunderstand that electrode function may affect the expansioncharacteristics of the composite material. As example, a polyacrylicacid may be expanded with an aqueous solution of hydrogen chloride.Exposure of this materials to sodium bicarbonate generates carbondioxide. Those experienced in the art will recognize that many differentacids may be used for similar purpose. In an additional example thatillustrates this embodiment an aqueous solution of ammonium chloride isused to expand polyacrylic acid particles. Exposure of this material tosolid sodium hydroxide pellets, generates ammonia gas. This gas may beused for cleaning operations as well as fuel cell operation. In theseexamples the water and soluble reaction products generated may also becontained by the composite material, avoiding the leaking of liquidsfrom the device used to conduct the fluid treatment operation.

In another particular embodiment of the invention, a composite materialis fabricated which is used to prepare cleaning solutions. Cleaningsolutions often contain surfactants and acidic or caustic agents thatare irritating to the user. For many applications these solutions areusually sold in concentrated form. The mixing and subsequent use of thecleaning fluids may pose a hazard even when prepared correctly. In thisembodiment concentrated cleaning solutions are used to expandpolyacrylic-polyacrylamide particles. When this composite material isexposed to water in a device as depicted, in FIGS. 1A, 1B, 1C, and 1D, acleaning solution ready for direct use is generated. These materials anddevices may safely store and allow application of the hazardoussolutions. These devices allow incorporation into mechanical systemssuch as sprayers.

In another embodiment of the invention, the composite material isconstructed to treat hydrocarbon fuels that are contaminated with waterand dissolved and suspended chemical and biological agents. Compositesmay be prepared to remove the water and associated contaminants and ifneeded simultaneously deliver biocidial agents.

In another embodiment of the invention, the composite material isconstructed to withstand sterilization. Sterilization processes includethermal processes, such as steam sterilization or other processeswherein the composite purification material is exposed to elevatedtemperatures or pressures or both, resistive heating, radiationsterilization wherein the composite purification material is exposed toelevated radiation levels, including processes using ultraviolet,infrared, microwave, and ionizing radiation, and chemical sterilization,wherein the composite purification material is exposed to elevatedlevels of oxidants or reductants or other chemical species, and which isperformed with chemicals such as halogens, reactive oxygen species,formaldehyde, surfactants, metals and gases such as ethylene oxide,methyl bromide, beta-propiolactone, and propylene oxide. Additionally,sterilization may be accomplished with electrochemical methods by directoxidation or reduction with microbiological components or indirectlythrough the electrochemical generation of oxidative or reductivechemical species. Combinations of these processes are also used on aroutine basis. It should also be understood that sterilization processesmay be used on a continuous or sporadic basis while the compositematerial is in use.

In another particular embodiment of the invention, a composite materialis fabricated for the sensing of microorganisms. Here, polyacrylic acidpolyacrylamide particles are expanded with a nutrient media thatsupports growth of bacteria. When the composite material is exposed toan aerosol containing bacteria the bacteria are adsorbed to the particlesurface. The nutrient solution contained by the particle allowspropagation of the organisms, as well as sensing, identification, andquantitation of the biological agents. Those experienced the art willrecognize that indicator agents may be used in the nutrient media orthat the nutrient media may be replaced with a detection media thatallows many different types of genetic screening to be completed. Thoseexperienced in the art will also recognize that the surface propertiesof the composite material may be modified for specific selection ofdifferent organisms as well as the stability of the interaction of theorganisms on the surface. Those experienced in the art will alsorecognize that other particle types can simultaneously be collected andthat the use of electrical charging of particles through a variety ofmechanisms can enhance the collection efficiency of devicesincorporating the materials of the invention.

In another particular embodiment of the invention, a composite materialis fabricated for the treatment of chemical weapons such as nerveagents. Here, polyacrylic acid polyacrylamide particles are expandedwith a solution that collects, neutralizes, and degrades chemical agentsand toxins. When the composite material is exposed to the chemical agentchemical reactions which reduce the toxicity of the chemical agentsoccur. Many of these reactions are exothermic and thus provide a basisfor sensing and monitoring the presence of the agents and theirdegradation. Monitoring these interactions can yield devices whichprovide information on chemical agent presence as well as providing anindicator for device “end of life” or remaining functional capacity.

In another particular embodiment of the invention, a composite materialis fabricated for the treatment of ground water in subsurface locations.Here polyacrylic acid-polyacrylamide particles are expanded with agentsthat react with contaminants in a fluid plume. These particles may bemixed with minerals such as apatites and with metals such aszero-valent-iron. The composite material may also be linked to areservoir that contains additional agents for replenishing the compositematerial. The advantages to the material and devices of this embodimentinclude the ability to deliver chemical agents in a spatially controlledand timed manner.

In general, the invention comprises a method and a means for fabricatingmaterials and devices for the treatment of fluid, and more specificallyfor the removal and conversion of contaminants, for the delivery ofagents, and for sensing and detection purposes. Fluids of particularinterest and importance include drinking water, beverage production,cleaning solution preparation, and breathing air. Agent generation ofparticular interest includes gases such as oxygen, chlorine dioxide,ammonia, and carbon dioxide. Contaminants that need to be removed fromdrinking water include, metals, microorganisms, pesticides, and thebyproducts of the disinfection process. Agents that need to be deliveredto beverages include flavorings, sweeteners, colorants, gases, andnutritional and medicinal agents.

A typical specific embodiment of an apparatus containing the compositematerial of the invention that incorporates a porous composite materialis now described. A removable housing is mated with a cap, the caphaving an inflow orifice and an outflow orifice. A water or air supplyconduit is joined to the inflow orifice to deliver non-treated water orair into the device, and a water or air discharge conduit is joined tothe outflow orifice to conduct treated water or air from the device.Water or air passes into the housing and the pressure of the water orair flow forces it through the porous composite material, that is formedin the shape of hollow cylinder with an axial bore, the treated water orair passing into the axial bore that connects to the outflow orifice. Itis to be understood that other configurations where water or air iscaused to pass through a porous composite material (which may havedifferent geometrical shapes and/or different flow properties) arecontemplated to be within the scope of the invention. The compositematerial is formed by placing both expanding and optional non-expandingmedia between two capped porous supports of which the outer supportlimits the outer diameter and the inner support is the central bore.Both supports are chosen to have a pore size smaller than the particlesused. In this specific embodiment the pore size of the supports is lessthan 300 microns and the support composition is polyethylene.

Multiple embodiments where the composite purification material of theinvention is used in the form of a sheet, fiber, film, web, or withindependent particles moving through a fluid, are envisioned. Acomposite material used in connection with normal flow-throughgeometries has the fluid being treated by passage through the sheet,fiber, film, web, particle or combinations thereof. Alternatively acomposite purification material may be used in connection with crossflowfiltration. Embodiments where the particles are loosely held orintroduced into a stream by injection, dropping, or other physicalmechanisms as well as magnetic and electrical field control mechanismsare possible. Collection of the injected particles allows identificationof contaminant level changes over periods of time. Likewise, movement oflong fibers allows temporal information to be obtained.

With reference to the drawings, the invention and a mode of practicingit will now be described with regard to several particular embodiments,which depict use of the composite materials of the invention and devicesincorporating materials of the invention.

FIG. 1A illustrates a typical specific embodiment of a cross flow fluidtreatment apparatus containing the composite material of the invention,which incorporates a porous block material that allows limited passageof fluid through the composite material. A removable housing 4 housesthe composite material 3 and is situated between fluid conduit 1(inflow) and treated fluid conduit 6. Fluid conduit 2 indicates outflowfor fluid conduit 1.

FIG. 1B illustrates a typical specific embodiment of a fluid treatmentapparatus containing the composite material of the invention, thatincorporates a porous block material that allows passage of fluidthrough the composite material. A removable housing 4 houses thecomposite material 3 and is situated between fluid conduit 1 (inflow)and treated fluid conduit 2.

FIG. 1C illustrates a typical specific embodiment of a cross-flow orflow-through fluid treatment apparatus containing the composite materialof the invention, that incorporates a porous block material that allowslimited passage of fluid through the composite material, and areservoir. A removable housing 4 houses the composite material 3 and issituated between fluid conduit 1 (inflow) and treated fluid conduit 6.Fluid conduit 2 indicates outflow for fluid conduit 1. Removable housing4 and composite material 3 are connected to a reservoir 5.

FIG. 1D illustrates a typical specific embodiment of a fluid treatmentapparatus containing the composite material of the invention, thatincorporates a porous block material that allows controlled passage offluid through the composite material as well as directing fluid flow. Aremovable housing 4 houses the composite material 3 and is situatedbetween fluid conduit 1 (inflow) and treated fluid conduit 2. Twodifferent fluid conduit 2 s are depicted, one where fluid is translatedthrough the composite material and one where fluid only has a limitedsurface interaction with the composite material. Removable housing 4 andcomposite material 3 could be connected to a reservoir as indicated inFIG. 1C, if desired.

FIG. 2A illustrates a typical specific embodiment of a fluid treatmentapparatus containing the composite material of the invention, thatincorporates a porous block material that allows passage of fluidthrough the composite material. A removable housing 4 houses thecomposite material 3 that has a central bore 7 for fluid 2 to exit(outflow). Fuid inflow 1 is through a cap on container 9 that housesremoval housing 4. This figure illustrates a standard radial flowdevice.

FIG. 2B illustrates a typical specific embodiment of a fluid treatmentapparatus containing the composite material of the invention, thatincorporates a porous block material that allows passage of fluidthrough the composite material. A removable housing 4 houses thecomposite material 3 that has a central bore 7 for fluid 2 to exit(outflow). Fuid inflow 1 is through a cap on container 9 that housesremoval housing 4. This figure illustrates a standard radial flowdevice. In this device the central bore 7 extends past the compositematerial housing 4 and reduces interaction with fluid inflow 1, and isone method of increasing flow and reducing contact with compositematerial 3.

FIG. 3A illustrates an embodiment where the composite material of theinvention is used in the form of a sheet or film. Composite material 3housing 4 is used to treat influent fluid 1. Two effluent fluids 2 existone that demonstrates a cross flow design and one that demonstrates aflow through design.

FIG. 3B illustrates an embodiment where the composite material of theinvention is used in the form of a sheet or film and wrapped around acentral bore 7. Composite material 3 and housing 4 is used to treatinfluent fluid 1. Two effluent fluids 2 exist one that demonstrates across flow design and one that demonstrates a flow through design.

FIG. 4A illustrates a typical specific embodiment of a fluid contaminantsensing apparatus (planar) containing the composite material of theinvention, which individual particles of the material that pass throughthe fluid to be sensed. A housing 4 contains both a reservoir and areceptacle for composite material particles 3. Fuid flow 1 interactswith particles falling in housing 4. Particles 3 may be guided by aporous mesh (no shown for clarity).

FIG. 4B illustrates a typical specific embodiment of a fluid contaminantsensing apparatus (cylindrical) containing the composite material of theinvention, which individual particles of the material that pass throughthe fluid to be sensed. A housing 4 contains both a reservoir anda-receptacle for composite material particles 3. Fluid flow 1 interactswith particles falling in housing 4. Particles 3 may be guided by aporous mesh (not shown for clarity).

FIG. 5A illustrates a typical specific embodiment of a fluid treatmentapparatus containing the composite material of the invention, whichindividual particles contained in a disposable single use package. Ahousing 4 contains composite material particles 3. When housing 4 andmaterial 3 is placed in contact with fluid 1 the contents of particles 3are released into fluid 1. This “tea-bag” example is illustrated with astring 10 for positioning.

FIG. 5B illustrates a typical specific embodiment of a fluid treatmentapparatus containing the composite material of the invention, whichindividual particles are placed loose into a housing 4. Fluid 1 isplaced in with particles 3 and plunger 11 that holds a porous materialis used to confine particles 3 when liquid is poured from housing 4. Ahousing 4 contains composite material particles 3. When particulatematerial 3 is placed in contact with fluid 1 the contents of particles 3are released into fluid 1. This “loose-coffee-maker” example isillustrated in a common configuration.

The following examples exemplify the type of composite materials thatmay be generated under the methods of the invention.

EXAMPLES Example 1

A beverage syrup containing phosphoric acid, coloring agents,sweeteners, and flavoring agents, was absorbed in an expandablepolyacrylic acid particle. The syrup was then released when exposed towater.

Example 2

An iodide solution was absorbed in an expandable polyacrylic acidparticle. A purple colored composite was generated. The color wasremoved when a solution containing ascorbic acid was exposed to thecomposite.

Example 3

The following acids were absorbed into an expandable polyacrylic acidparticle: hydrochloric, phosphoric, sulfuric, hydrofluoric, citric, andboric. The composites were stable for many days.

Example 4

The following bases were absorbed into an expandable polyacrylic acidand polyacrylamide-polyacrylic acid particles: sodium hydroxide,ammonium hydroxide, and potassium hydroxide. The composites were stablefor many days.

Example 5

The following salt solutions were absorbed into an expandablepolyacrylic acid and polyacrylamide-polyacrylic acid particles: sodiumchloride, sodium bicarbonate, silver nitrate, and calcium chloride. Thecomposites were stable for many days.

Example 6

Nanometer size particles of reduced silver were generated withexpandable polyacrylic acid and polyacrylamide-polyacrylic acidparticles using silver nitrate and irradiation. Composite color wastunable based upon parameters used and included blues and reds. When thecomposite material was exposed to tap water silver chloride was formed.After a period of time silver ion was generated.

Example 7

The following metal ion solutions were absorbed into an expandablepolyacrylic acid-polyacrylamide particle, copper, iron, lanthanum, andaluminum. The composites could be dried and re-expanded upon exposure tofluid.

Example 8

A mixed ionic flocculating solution was absorbed into an expandablepolyacrylic acid-polyacrylamide particle. The flocculating agent wasreleased upon exposure to fluid.

Example 9

A potassium permanganate solution was absorbed into an expandablepolyacrylic acid-polyacrylamide particle. Manganese oxide(s) was formedin the process. Dried composite particles expanded when exposed tofluid. When composite particles were exposed to hydrogen peroxide,oxygen gas was generated.

Example 10

A hydrochloric acid solution was absorbed into an expandable polyacrylicacid-polyacrylamide particle and when exposed to solid sodiumbicarbonate, carbon dioxide evolved.

Example 11

A hydrochloric acid solution was absorbed into an expandable polyacrylicacid-polyacrylamide particle and when exposed to solid sodium chlorite,chlorine dioxide evolved.

Example 12

A sodium thiosulfate solution was absorbed into an expandablepolyacrylic acid particle. When the composite was exposed to a solutioncontaining hypochlorous acid the acid was neutralized.

Example 13

An alcoholic solution containing a mixture of vitamins was absorbed intoan expandable polyacrylic acid particle. The composite was stable formany days.

Example 14

A concentrated solution of monoethanolamine was absorbed into anexpandable polyacrylic acid particle. The composite was stable for manydays.

Example 15

A concentrated solution of octenol, an insect attractant was absorbedinto an expandable polyacrylic acid particle. The composite was stablefor many days.

Example 16

A solution containing cyclodextrins and odor neutralizing compounds wasabsorbed into an expandable polyacrylic acid particle. The composite wasstable for many days.

Example 17

A solution containing sodium bicarbonate absorbed into an expandablepolyacrylic acid particle, and when exposed to calcium ion calciumcarbonate formed.

Example 18

Tap water was absorbed into an expandable polyacrylicacid-polyacrylamide particle and frozen. Upon warming, the compositereturned to a hydrated form.

Example 19

The following oxidizers were absorbed into an expandable polyacrylicacid and polyacrylamide-polyacrylic acid particles: hypochlorous acid,sodium monopersulfate, stabilized chlorine, and hydrogen peroxide. Thestability of the composite was determined by oxidizer concentration andenvironmental parameters.

Example 20

A solution containing a dissolved aspirin tablet was absorbed into anexpandable polyacrylic acid particle. The composite was stable for manydays.

Example 21

A solution containing ethylenediaminetetraacetic acid (EDTA) wasabsorbed into an expandable polyacrylic acid particle. The composite wasstable for many days.

Example 22

An eye care solution containing saline, boric acid, and borate, as wellas a disinfectant was absorbed into an expandable polyacrylic acidparticle. The composite was stable for many days.

Example 23

A dental/oral care solution containing alcohol, flavoring, coloring, andplaque treatment agent, was absorbed into an expandable polyacrylic acidparticle. The composite was stable for many days.

Example 24

A biodegradable cleaning solution containing polyethylene glycol,ethers,modified sulfonates, and coloring agents, was absorbed in concentratedform into polyacrylic acid particles. The composite was stable for manydays.

As described above, the composite material and mixtures of differentcomposite materials of the invention are extremely useful in the area ofcontaining or storing chemical species for reaction of or delivery intofluids. Composites when exposed to fluids may release their contentsunder controlled situations, may generate gases, may interact withradiation, may react with species in the fluid stream and in many casesmay be used in a reversible manner or recharged for further use. Thecomposites are useful in both gas filtration and liquid purification,particularly in the area of purifying breathable air and drinking water.Because of the high efficiency and simplicity with which the compositematerials of the present invention may function the materials of theinvention are useful in many industries and consumer products, andappliances. Specifically, the products may be used in drinking waterapplications, passive air treatment application, forced airapplications, humidification and dehumidification systems, water usedfor recreational purposes, such as water used in swimming pools, hottubs, and spas. The materials may be used in appliances such asrefrigerators, fluid coolers/chillers, water fountains, and beveragedispensing systems. They may be used in cleaning systems that useautomatic washers, manual washers, high pressure sprayers, and the like.

As the result of the ability of the material of the invention toefficiently collect, immobilize, and provide a platform formicroorganism and other biological agents sensing, it has numerousapplications in both civilian and military defense applications.Further, the material of the invention can house reactive solutionswhich can collect, isolate, detect, neutralize, and degrade chemicaltoxins.

The pharmaceutical and medical fields may use materials of the inventionto treat blood, surgical fluids, wounds, and provide protective devicesfor both patient and attendant. The eye care, lens care, dental care,and oral care fields may utilize the materials of the invention Thematerial may also be used in hospital, industrial areas, or enclosedareas requiring highly purified air having extremely low content ofmicroorganisms, e.g., in intensive care wards, operating theaters, andclean rooms used for the therapy of immunosuppressed patients, or inindustrial clean rooms used for manufacturing electronic andsemiconductor equipment.

The material of the invention has multiple uses in fermentationapplications and cell culture, where it may be used to removemicroorganisms from aqueous fluids, such as fermentation broths orprocess fluids, allowing these fluids to be used more efficiently andrecycled, e.g., without cross-contamination of microbial strains. Inaddition, because the material is so efficient at removingmicroorganisms and at retaining them once removed, it may be used as animmobilization medium for enzymatic and other processing requiring theuse of microorganisms. A seeding solution containing the desiredmicroorganisms is first forced through the material of the invention,and then substrate solutions, e.g., containing proteins or othermaterials serving as enzymatic substrates, are passed through the seededmaterial. As these substrate solutions pass through the material, thesubstrates dissolved or suspended therein come into contact with theimmobilized microorganisms, and more importantly, with the enzymesproduced by those microorganisms, that may then catalyze reaction of thesubstrate molecules. The reaction products may then be eluted from thematerial by washing with another aqueous solution.

The material of the invention has numerous other industrial uses, e.g.,treating water used in cooling systems. Cooling water often passesthrough towers, ponds, or other process equipment where contaminants maycome into contact with the fluid.

Similarly, breathable air is often recycled in transportation systems,either to reduce costs (as with commercial airliners) or because alimited supply is available (as with submarines and spacecraft).Efficient removal of contaminants permits this air to be recycled moresafely. In addition, the material of the invention may be used toincrease indoor air quality in homes, buildings, enclosed areas, andprotective shelters, in conjunction with the air circulation andconditioning systems already in use therein. The composite material ofthe invention may also be used to purify other types of gases, such asanesthetic gases used in surgery or dentistry (e.g., nitrous oxide),gases used in the carbonated beverage industry (e.g., carbon dioxide),gases used to purge process equipment (e.g., nitrogen, carbon dioxide,argon), and/or to remove particles from surfaces, etc.

The composite materials of the invention may be used to generatecatalytic devices based upon chemicals such as metals, metal oxides, andbiochemical agents such as enzymes. These devices may be used to treator remediate emission gases such as those generated by the chemical,mining, power, and manufacturing industries as well as those generatedfrom consumer products such as those powered with combustion engines.They may be used to generate gases for specific applications such asoxygen for respiration.

In each of these applications, the method of using the material of theinvention is relatively simple and should be apparent to those of skillin the filtration art. The fluid to be treated is simply conducted toone side of the composite material of the invention, typically disposedin some form of housing, and forced through the material as the resultof a pressure drop across the composite purification material, orconducted across the surface. Treated fluid is then conducted away fromthe “exit” side of the material and further processed or used.

The invention having been thus described by reference to certain of itsspecific embodiments, it will be apparent to those of skill in the artthat many variations and modifications of these embodiments may be madewithin the spirit of the invention, that are intended to come within thescope of the appended claims and equivalents thereto.

1-61. (canceled)
 62. The composite material of claim 57, wherein thematerial removes a gas containing elements selected from the followinggroup, oxygen, nitrogen, sulfur, and carbon.
 63. The composite materialof claim 62, wherein the material removes an acid gas.
 64. The compositematerial of claim 62, wherein the material removes an organismincapacitating gas. 65-68. (canceled)
 69. The composite material ofclaim 26 wherein the material generates a gas when exposed to situationsselected from the following group, exposure to chemical agents, exposureto biological agents, exposure to radiation, exposure to temperaturechanges, or a combination thereof.
 70. The composite material of 69wherein the material generates a gas selected from the following group,oxidizers, components of breathing air, anesthetics, incapacitants, fuelsources, or combinations thereof.
 71. The composite material of 70wherein the material generates a gas selected from the following group,halogens, oxygen, chlorine dioxide, carbon dioxide, nitrogen, hydrogen,and combinations thereof.
 72. The composite material of claim 26comprising a plurality of composite materials that, when placed incontact with a common fluid, generate a gas, liquid, solid, orcombination thereof. 73-84. (canceled)